KR101886911B1

KR101886911B1 - Black photo sensitive resin composition, a color filter comprising a black metrics and/or a column spacer prepared by using the composition, and a liquid crystal display comprising the color filter

Info

Publication number: KR101886911B1
Application number: KR1020150042272A
Authority: KR
Inventors: 이재을; 조승현; 최한영
Original assignee: 동우 화인켐 주식회사
Priority date: 2015-03-26
Filing date: 2015-03-26
Publication date: 2018-08-08
Also published as: KR20160115149A

Abstract

The present invention relates to a colorant composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) an adhesion promoter, and (F)
(E) the adhesion promoter comprises a silane compound represented by the general formula (1), a color filter comprising a black matrix and / or a column spacer manufactured using the black photosensitive resin composition, and a color filter A liquid crystal display device comprising:
[Chemical Formula 1]

Description

TECHNICAL FIELD [0001] The present invention relates to a black photosensitive resin composition, a color filter including a black matrix and / or a column spacer manufactured using the same, and a liquid crystal display device including the color filter. A COLUMN SPACER PREPARED BY USING THE COMPOSITION, AND A LIQUID CRYSTAL DISPLAY COMPRISING THE COLOR FILTER}

The present invention relates to a black photosensitive resin composition, a color filter including a black matrix and / or a column spacer manufactured using the same, and a liquid crystal display including the color filter.

The color filter is composed of three primary color pixels of a red pixel, a green pixel and a blue pixel, and a black matrix formed at the boundary of each color pixel and not transmitting substantially visible light as black. The black matrix or black column spacer is a material for securing the space required for moving the liquid crystal between the two glass plates constituting the LCD and maintaining the elasticity of the LCD, and is formed of a black photosensitive resin composition. The black matrix or black column spacers can be installed in any desired position in a column shape, allowing for precise spacing and thickness control. In this case, it is necessary to adjust the height of the black column spacer in consideration of the height of the device.

Conventionally, in order to form a black column spacer, a method of dispersing bead particles which become spacers on the entire surface of a substrate has been adopted. However, this method has a disadvantage in that it is difficult to uniformly maintain the cell gap, and the bead is attached to the pixel display portion, resulting in lower contrast and image quality of the image. In order to solve these problems, various methods using a photosensitive resin composition capable of forming a step difference have been proposed.

Korean Patent Laid-Open Publication No. 10-2012-033893 discloses a method of forming a black column spacer having a height difference by using a photosensitive resin composition, but has a disadvantage that the adhesion of the film is not sufficient.

Korean Patent Publication No. 10-2012-033893

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a black photosensitive resin composition having excellent physical properties such as optical density, electrical insulation, light- .

It is another object of the present invention to provide a color filter including a black matrix and / or a column spacer manufactured using the black photosensitive resin composition, and a liquid crystal display device having the color filter.

In order to achieve the above object,

The present invention relates to a colorant composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) an adhesion promoter, and (F)

Wherein the adhesion promoter (E) comprises a silane compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

In this formula,

X is a vinyl group, an epoxy group, an amino group, a (meth) acrylic group, a mercapto group, a sulphido group, an isocyanate group or an alkyl halide group;

Wherein R 1 is a straight or branched alkylene group having 6 to 20 carbon atoms which is substituted or unsubstituted with a straight or branched alkyl group having 1 to 6 carbon atoms and wherein the alkylene group is substituted by at least one hetero atom or an ester group, Connected chain;

R2 to R4 each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and at least one of R2 to R4 is an alkoxy group having 1 to 5 carbon atoms.

The present invention also provides a color filter comprising a black matrix or a column spacer manufactured using the black photosensitive resin composition.

The present invention also provides a liquid crystal display device having the color filter.

The black photosensitive resin composition of the present invention satisfies generally required optical density, electrical insulation, light shielding property, heat resistance and the like, and particularly provides an effect of greatly improving adhesion.

Further, a color filter including a black matrix and / or a column spacer manufactured using the black photosensitive resin composition as described above, and a liquid crystal display device including the color filter provide excellent properties in terms of driving performance and durability.

The black adhesion promoter (E) comprises a silane compound represented by the following formula (1):

[Chemical Formula 1]

In this formula,

X is a vinyl group, an epoxy group, an amino group, a (meth) acrylic group, a mercapto group, a sulphide group, an isocyanate group or an alkyl halide group,

When a black photosensitive resin composition is coated on a substrate and cured to form a pattern, a silane compound used as an adhesion promoter reacts with a binder resin (alkali-soluble resin) in a part of functional groups, and the remainder reacts with polar groups By doing so, it is known to perform the role of enhancing the adhesion between the pattern and the substrate.

However, conventionally used silane compounds have problems such as failure to overcome the steric hindrance of the side chains introduced into the binder resin, resulting in insufficient number of functional groups capable of reacting with polar groups on the surface of the substrate, There was a problem that I could not contribute.

The black photosensitive resin composition of the present invention comprises a silane compound having a structure in which a long straight chain having a functional group (X) capable of reacting with and bonding with a polar group on the surface of the substrate is bonded to an alkoxysilanyl group, Thereby solving the above-mentioned problem. That is, a long straight-chain chain having a functional group (X) capable of reacting with the polar group of the surface of the substrate at the end of the substrate passes through the steric hindrance of the side chains introduced in the binder resin or the interferences of other substituents, (In this case, the alkoxysilanyl group is bonded to the binder resin). In this case, the adhesion between the binder resin and the substrate surface is significantly improved.

Each component constituting the black photosensitive resin composition of the present invention will be described below. However, the present invention is not limited to these components.

The colorant (A)

The colorant is used for black implementation and imparts light shielding to both the black matrix and the spacer. That is, the black matrix serves to prevent the light leakage, and the spacer can prevent the malfunction of the device caused by the light generated from the outside.

As the colorant, any colorants known in the art such as organic pigments, dyes and black pigments can be used as long as they have light shielding properties in visible light, but it is preferable to use black pigments.

As the black pigment, any known black pigments may be used without particular limitation, and specifically, aniline black, perylene black, titanium black, carbon black and the like may be used. These may be used singly or in combination of two or more. Examples of the carbon black include channel black, furnace black, thermal black and lamp black.

Carbon black coated with a resin on its surface may be used for electrical insulation if necessary. In addition, since the resin-coated carbon black has a lower conductivity than carbon black not coated with the resin, excellent electrical insulation can be imparted to the black matrix, the spacer, or the black matrix integrated spacer.

In addition, the colorant may further optionally include a color correcting agent. As the color correcting agent, condensation polycyclic pigments such as anthraquinone pigments or perylene pigments, phthalocyanine pigments or organic pigments such as azo pigments can be used.

The colorant may be contained in an amount of 1 to 50% by weight, preferably 5 to 20% by weight based on the total weight of the black photosensitive resin composition. If the content of the colorant is less than the above range, the light shielding property is not sufficient and the above-mentioned effect can not be ensured. On the other hand, if the content exceeds the above range, the quality of the pattern obtained after patterning may deteriorate. .

(B) an alkali-soluble resin

The alkali-soluble resin has reactivity and alkali solubility due to the action of light or heat, acts as a dispersion medium for solids including a colorant, and may be selected from resins known in the art without any particular limitations as long as it functions as a binder resin have.

Preferably, a cadmium resin is used so as to secure a low dielectric constant. Specifically, examples of the cardboard resin include bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis , Bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis Bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) methane, bis Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) Bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, , 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9- Bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9- , 5-dibromophenyl) fluorene, etc. These may be used singly or in combination of two or more.

The alkali-soluble resin preferably has an acid value of 20 to 200 (KOH mg / g). The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and is concerned with the solubility of the resin. When the acid value of the resin falls within the above range, the solubility in the developer is improved to easily dissolve the non-exposed portion and increase the sensitivity, so that the pattern of the exposed portion remains during development, thereby improving the film remaining ratio.

In order to improve the surface hardness of the alkali-soluble resin, the molecular weight and molecular weight distribution (MW / MN) may be limited. Preferably, the weight average molecular weight is 3,000 to 200,000, more preferably 5,000 to 100,000, still more preferably 5,000 to 30,000. It is preferable that the resin is directly polymerized or purchased so that the molecular weight distribution is 1.5 to 6.0, more preferably 1.8 to 4.0.

The alkali-soluble resin having the molecular weight and molecular weight distribution in the above range is preferable because it can improve the hardness and the high residual film ratio as well as the solubility of the non-exposed portion in the developer and improve the resolution.

The alkali-soluble resin may be used in an amount of 5 to 80% by weight, preferably 7 to 50% by weight based on the total weight of the black photosensitive resin composition. Such a content is a range selected considering various factors such as solubility in a developing solution, pattern formation, etc. When used within the above range, solubility in a developing solution is sufficient and pattern formation is easy, So that the dropout of the non-pixel portion is improved.

(C) Photopolymerization compound

The photopolymerizable compound is a component for enhancing the strength of the pattern, and examples thereof include monofunctional, bifunctional or polyfunctional multimers, and preferably monomers having two or more functionalities. For example, a monofunctional acrylate such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N-vinylpyrrolidone Monomer; (Meth) acrylates such as 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di Bifunctional monomers such as 3-methylpentanediol di (meth) acrylate or 3-methylpentanediol di (meth) acrylate; (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, and the like. These may be used alone or in combination of two or more.

The photopolymerizable compound may be used in an amount of 1 to 30% by weight, preferably 2 to 15% by weight based on the total weight of the black photosensitive resin composition. Such a content range is a range determined in consideration of various factors such as strength or smoothness as a black matrix or a spacer to be finally obtained. If the content is less than the above range, strength and smoothness are insufficient and conversely, , There arises a problem that patterning is not easy due to high strength, and therefore, it is appropriately used within the above range.

(D) Light curing Initiator

The photopolymerization initiator is a compound for initiating the polymerization of the photopolymerizable compound and is not specifically limited in the present invention, but may be an acetophenone, benzophenone, triazine, thioxanthone, oxime, benzoin, anthraquinone, Imidazole-based compounds, etc. These may be used alone or in combination of two or more.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2- Oligomers of benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2- methyl [4- (1-methylvinyl) phenyl] propan- Among them, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one can be preferably used.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, Bis (diethylamino) benzophenone, and the like.

Examples of the triazine compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2 - (p-methoxyphenyl) -4,6-bis -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6 (Trichloromethyl) -s-triazine, 2- (4-methoxynaphtho 1-yl) -4,6-bis (trichloromethyl) (Piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propanecioxanthone. have.

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, and OXE01 and OXE02 commercially available from BASF.

Examples of the benzoin compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the anthraquinone-based compounds include 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone.

Examples of the nonimidazole-based compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, a phenyl group in the 4,4', 5,5 'position is bonded to a carboalkoxy group And an imidazole compound substituted by a halogen atom.

Such a photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight based on the total weight of the black photosensitive resin composition. Such a content range takes into consideration the photopolymerization rate of the photopolymerizable compound and the physical properties of the resultant coating film. If the amount is less than the above range, the polymerization rate is low and the overall process time may be prolonged. On the other hand, Since the physical properties of the coating film may be lowered, it is suitably used within the above range.

The photopolymerization initiator may be used in combination with a photopolymerization initiator. When the photopolymerization initiator is used in combination with the photopolymerization initiator, the black photosensitive resin composition containing the photopolymerization initiator is more preferable because productivity is improved when the support spacer for holding the cell gap is formed by using the black photosensitive resin composition.

The photopolymerization initiation auxiliary may be used for increasing the polymerization efficiency, and amine compounds, alkoxyanthracene compounds, and thioxanthone compounds may be used.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, benzoic acid- (Dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'-bis (diethylamino) benzoate, 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, Phenanone, 4,4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- And the like.

The photopolymerization initiator may be directly produced or commercially available. For example, a trade name of "EAB-F" [manufactured by Hodogaya Chemical Industry Co., Ltd.] may be used.

The photopolymerization initiator is preferably used in an amount of usually not more than 10 mol, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When the photopolymerization initiator is used within the above range, the polymerization efficiency can be increased and the productivity improvement effect can be expected.

(E) adhesion promoter

The adhesion promoter functions to make the pattern made of the black photosensitive resin composition more closely adhered to the substrate.

In the present invention, the adhesion promoter includes a silane compound represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

In the silane compound of Formula 1, the hetero atom may be, for example, a sulfur, phosphorus, oxygen or nitrogen atom.

From the viewpoint of improving the adhesion of the black matrix and the column spacer pattern, it is preferable that R ₂ to R ₄ in the general formula (1) are all alkoxy groups.

Specifically, the silane compound of formula (1) may be a compound represented by the following formulas (2) to (7). These may be used alone or in combination of two or more.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

The (E) adhesion promoter may be contained in an amount of 0.01 to 7% by weight, preferably 0.5 to 5% by weight, more preferably 0.5 to 2% by weight based on the total weight of the black photosensitive resin composition. If the content is less than 0.01% by weight, the effect of improving the adhesion may be insignificant. If the content is more than 5% by weight, the cohesive strength may be excessively increased and the adhesion may be deteriorated.

The (E) adhesion promoter may be composed only of the silane compound of Formula 1, and the silane compound of Formula 1 may be used together with other silane coupling agents. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 2- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Ethoxy silane, and the like.

(F) Solvent

The solvent may be any solvent capable of dissolving or dispersing the above-mentioned composition, and is not particularly limited in the present invention. Preferably, an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness can be used.

Representative examples of usable solvents include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Ryu; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as? -butyrolactone.

Among the above solvents, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate may be preferably used, and propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used. These solvents may be used singly or in combination of two or more.

The solvent may be contained in a balance such that the black photosensitive resin composition satisfies 100 wt%. Such a content is selected in consideration of dispersion stability of the composition and easiness of process in the production process (for example, applicability). In other words, the black photosensitive resin composition according to the present invention can produce a black matrix, a spacer, or a black matrix-integrated spacer by wet coating, wherein the wet coating method is a roll coater, a spin coater, a slit and spin coater, Or a die coater), a coating device such as an inkjet can be used.

(G) Additive

The black photosensitive resin composition of the present invention may further contain additives known in the art for various purposes. Such additives include dispersants, fillers, other polymer compounds, ultraviolet absorbers, anti-aggregation agents, and the like. These additives may be used singly or in combination of two or more, and it is preferable to use not more than 5% by weight based on the total weight of the black photosensitive resin composition in consideration of light efficiency and the like.

As the dispersing agent, a commercially available surfactant may be used, and a fluorine-based surfactant , a urethane-based surfactant , or the like may be used. Examples of the fluorine-based surfactant include BM-1000, BM-1100 (BM Chemie), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA / -190 / SZ- Ltd.) and the like can be used. The urethane surfactant includes DiperBYK-163 (BYK). Dispersion aids such as Solsperse 5000 (Lubrisol) may also be added.

Examples of the filler include glass, silica and alumina. Other polymer compounds include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate , Polyester, polyurethane and the like can be used.

Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone. Examples of the antiflocculating agent include sodium polyacrylate .

The production of the black photosensitive composition of the present invention is not particularly limited and follows the known production method of the photosensitive composition.

For example, a coloring agent may be added to a solvent, followed by addition of the rest of the composition and other additives, followed by stirring. At this time, the colorant may be added in the form of a mill base in which a pigment or the like is dissolved or dispersed in advance in a solvent or an alkali-soluble resin. The additive, if in solution form, may be added in advance to the solvent along with the colorant.

The thus-prepared black photosensitive resin composition can be preferably used for the production of a display device, preferably a black matrix of a liquid crystal display, a spacer for holding a cell gap, or a black matrix integrated spacer.

In particular, the black photosensitive resin composition of the present invention can be preferably used for producing a black matrix-integrated spacer, and the black matrix-integrated spacer does not form a black matrix and a spacer but forms a black matrix and a spacer All of which can be performed.

The present invention also relates to a color filter comprising a black matrix and / or a column spacer made using the black photosensitive resin composition.

Further, the present invention relates to a liquid crystal display device including the color filter

A typical patterning process for forming a black matrix, spacer or black matrix integrated spacer according to the photolithography method comprises the following steps:

a) applying a black photosensitive resin composition to a substrate;

b) prebaking step of drying the solvent;

c) applying a photomask onto the obtained film to irradiate an actinic ray to cure the exposed portion;

d) performing a developing step of dissolving the unexposed portion using an aqueous alkali solution; And

e) drying and post-baking steps

A glass substrate or a polymer plate is used as the substrate. As the glass substrate, in particular, soda lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz can be preferably used. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

The coating may be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (which may be referred to as a die coater), an ink jet or the like so as to obtain a desired thickness.

Prebaking is performed by heating with an oven, a hot plate or the like. At this time, the heating temperature and the heating time in the pre-baking are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 150 ° C for 1 to 30 minutes.

The exposure performed after the pre-baking is performed by an exposure machine, and exposed through a photomask to expose only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

Alkali development after exposure is carried out for the purpose of removing the photosensitive resin composition in the portion where the non-exposed portion is not removed, and a desired pattern is formed by this development. As the developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal may be used. Particularly, a weakly alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate is used at a temperature of 10 to 50 ° C, preferably 20 to 40 ° C, using a developing machine or an ultrasonic cleaner .

The post bake is performed to enhance the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 220 ° C for 10 to 120 minutes. Post-baking Pre-baking is carried out using an oven, hot plate or the like.

At this time, the thickness of the black matrix is preferably 0.2 to 20 占 퐉, more preferably 0.5 to 10 占 퐉, and particularly preferably 0.8 to 5 占 퐉.

The film thickness of the column spacer and the black matrix integrated spacer is preferably 0.1 mu m to 8 mu m, more preferably 0.1 mu m to 6 mu m, and particularly preferably 0.1 mu m to 4 mu m.

The black matrix, the spacer or the black matrix integrated spacer made of the black photosensitive resin composition of the present invention is excellent in physical properties such as optical density, adhesion, electrical insulation and light shielding property, and is excellent in heat resistance and solvent resistance, It is possible to improve the reliability.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Manufacturing example 1: Preparation of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. As a monomer dropping lot, a mixture 40 of 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meth) acrylate in a molar ratio of 50:50 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) And stirring was prepared.

To this mixture, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added by a chain transfer agent dropping funnel to prepare a stirrer.

Then, 395 parts by weight of PGMEA was added to the flask, and the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring.

The dropping of monomer and chain transfer agent was then initiated. The mixture was allowed to stand at 90 DEG C for 2 hours, elevated to 110 DEG C after 1 hour, and maintained for 5 hours to obtain a resin having a solid acid value of 100 mgKOH / g.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin were measured by GPC method and HLC-8120GPC (manufactured by Tosoh Corporation) was used.

For the measurement conditions, TSK-GELG4000HXL and TSK-GELG2000HXL columns were connected in series and the temperature of the column was set at 40 ° C. Tetrahydrofuran was used as mobile phase solvent and flow rate was measured at 1.0 mL / min flow rate. The concentration of the measurement sample was 0.6% by weight, and the injection amount was 50 이며, and analyzed using an RI detector. As the standard materials for calibration, TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION) The average molecular weight was measured.

The weight average molecular weight measured by GPC in terms of polystyrene was 17,000 and the molecular weight distribution (Mw / Mn) was 2.3.

Manufacturing example 2: Silane compound Produce

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

2-1. 2 Silane compound Synthesis (D-1)

[Reaction Scheme 1]

An intermediate compound containing an epoxy group and a vinyl group was synthesized by reacting hex-5-en-1-ol (TCI) with epichlorohydrin, Using the addition reaction of silane and an intermediate compound, a silane compound of formula (2) was obtained.

2-2. (3) Silane compound Synthesis (D-2)

[Reaction Scheme 2]

Except that hex-5-enoic acid (TCI) was used in place of hex-5-en-1-ol, the reaction was carried out in the same manner as in Production Example 2-1, Silane compound.

2-3. 4 Silane compound Synthesis (D-3)

[Reaction Scheme 3]

The silane compound of formula (4) was obtained by the addition reaction of hydrosilane and 2-oct-7-enyl-oxirane (TCI) using a Pt catalyst.

2-4. Synthesis of silane compound of formula (5) (D-4)

[Reaction Scheme 4]

Except that oct-7-en-1-ol (TCI) was used in place of hex-5-en-1-ol To obtain a silane compound of the formula (5).

2-5. Synthesis of silane compound of formula (6) (D-5)

[Reaction Scheme 5]

The reaction was carried out in the same manner as in Production Example 2-1 except that dec-9-enoic acid (TCI) was used in place of hex-5-en-1-ol to obtain the compound of Formula 6 &Lt; / RTI >

2-6. Synthesis of silane compound of formula (7) (D-6)

[Reaction Scheme 6]

Except that de-9-en-1-ol (TCI) was used in place of hex-5-en-1-ol To obtain a silane compound of the formula (7).

Example 1 to 7 and Comparative Example 1 to 3: Preparation of black photosensitive resin composition

After a solvent was added to the mixer, a pigment, a silane compound, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and other additives were added and uniformly mixed by stirring to prepare a black photosensitive resin composition. The composition was as shown in Table 1 below.

The obtained photosensitive resin composition was coated on a glass substrate by a spin coating method, and then placed on a heating plate and maintained at a temperature of 100 캜 for 2 minutes to remove the solvent.

Then, the thin film was irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 40 mJ / cm 2 using an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Usuo Denki Co., Ltd., and no special optical filter was used.

The UV-irradiated thin film was developed with a developing solution of KOH aqueous solution having a pH of 12.5 for 60 seconds by using a spraying developer, and then heated in a heating oven at 220 ° C for 20 minutes to prepare a pattern. The thickness of the film prepared above was 3.0 mu m.

Composition (% by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pigment Pigment A ¹⁾ 0.77 0.77 0.77 0.77 0.77 0.77 0.77 0.77 0.77 0.77 Pigment B ²⁾ 8.53 8.53 8.53 8.53 8.53 8.53 8.53 8.53 8.53 8.53 Pigment C ³ ⁾ 1.71 1.71 1.71 1.71 1.71 1.71 1.71 1.71 1.71 1.71 additive Silane compound D-1 ⁴⁾ 1.00 5.50 Silane Compound D-2 ⁵⁾ 1.00 Silane Compound D-3 ⁶⁾ 1.00 Silane compound D-4 ⁷⁾ 1.00 Silane Compound D-5 ⁸⁾ 1.00 Silane Compound D-6 ⁹⁾ 1.00 Silane Compound D-7 ¹⁰⁾ 1.00 Silane compound D-8 ¹¹⁾ 1.00 Alkali-soluble resin Production Example 1 Resin 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 Photopolymerizable compound Kayarad DPHA ¹² ⁾ 2.22 2.22 2.22 2.22 2.22 2.22 2.22 2.22 2.22 2.22 Photopolymerization initiator Irgacure OXE-02 ¹³⁾ 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 Surfactants DiperBYK-163 ¹⁴⁾ 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Dispersant Solsperse 5000 ¹⁵⁾ 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 menstruum PGMMEA ¹⁶ ⁾ Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance

week)

1) Red 179, manufactured by DIC

2) Blue 15: 6, manufactured by DIC

3) CB (MA-8), product of Mitsubishi

4)

5)

6)

7)

8)

9)

10)

11)

12) Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

13) 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone- 1- (O- acetyloxime)

14) Manufactured by BYK

15) Products of Lubrisol

16) Propylene glycol monomethyl ether acetate

Test Example 1: Evaluation of pattern adhesion

In the film samples obtained in the above Examples and Comparative Examples, 11 lines each having a width of 1 mm and a length of 11 lines were drawn to form 100 lattice cells each having a width of 1 mm and a length of 1 mm. The 3M tape was adhered to the formed cell and strongly strongly peeled once in the vertical direction. Subsequently, the 3M tape was once again adhered and pulled strongly once in the vertical direction to perform peeling test, and the adhesion was evaluated according to the following criteria.

&Amp; cir &: The number of peeled cells is 5 or less

○: The number of peeled cells is 6 to 10

DELTA: Number of peeled cells 11 to 20

X: Number of peeled cells is 21 or more

division Adhesion Example 1 ◎ Example 2 ◎ Example 3 ◎ Example 4 ◎ Example 5 ◎ Example 6 ◎ Example 7 ○ Comparative Example 1 △ Comparative Example 2 △ Comparative Example 3 △

As shown in Table 2, only a very small number of cells were peeled from the patterns formed of the black photosensitive resin compositions (including the silane compound of Formula 1) of Examples 1 to 7 of the present invention. From these results, it can be confirmed that the pattern formed from the black photosensitive resin composition of the present invention has excellent adhesion to the substrate.

On the other hand, it was confirmed that the patterns formed of the black photosensitive resin compositions (including the silane compound of Formula 1) of Comparative Examples 1 to 3 were peeled off a large number of cells and insufficient adhesion to the substrate.

Claims

(A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) an adhesion promoter, and (F)
The black photosensitive resin composition according to claim 1, wherein the (E) adhesion promoter comprises a silane compound represented by formula (1)
[Chemical Formula 1]

In this formula,
X is an epoxy group or a (meth) acrylic group;
Wherein R 1 is a linear or branched alkylene group having 6 to 20 carbon atoms which is substituted or unsubstituted with a straight chain alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms and the alkylene group is substituted with at least one hetero atom or an ester group A chain in which two or more alkylene groups are connected;
R2 to R4 each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and at least one of R2 to R4 is an alkoxy group having 1 to 5 carbon atoms.

The black photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) has a weight average molecular weight of 3,000 to 200,000.

(A) 1 to 50% by weight of a colorant, (B) 5 to 80% by weight of an alkali-soluble resin, (C) 1 to 30% by weight of a photopolymerizable compound, (D) (F) 0.01 to 10% by weight of a photopolymerization initiator, 0.01 to 7% by weight of an adhesion promoter (E), and 100% by weight of the total composition.

4. The black photosensitive resin composition according to claim 3, wherein the colorant (A) is at least one selected from the group consisting of aniline black, perylene black, titanium black, and carbon black.

The black photosensitive resin composition according to claim 1, further comprising at least one additive selected from the group consisting of a dispersant, a filler, another polymer compound, an ultraviolet absorber, and an anti-aggregation agent.

A color filter comprising a black matrix or a column spacer made of the black photosensitive resin composition according to any one of claims 1 to 5.

A liquid crystal display device comprising the color filter of claim 6.